Stabilizer mixture

ABSTRACT

A stabilizer mixture containing
         (A) a sterically hindered amine compound, and   (B) two different compounds selected from the group consisting of an organic salt of Zn, an inorganic salt of Zn, an organic salt of Mg and an inorganic salt of Mg;
           the weight ratio of the two different compounds being 1:10 to 10:1;   with the provisos that   
           (1) the stabilizer mixture is essentially free of perchloric acid, and   (2) the two compounds in component (B) are different from the combination ZnO and Zn stearate and the combination ZnO and hydrotalcite;   is useful for stabilizing an organic material, in particular a polyolefin, against degradation induced by light, heat or oxidation.

This is a continuation of application Ser. No. 10/085,221 filed Feb. 28,2002, now abandoned, which is a continuation of application Ser. No.09/811,960 filed Mar. 19, 2001, now abandoned, which is a continuationof application Ser. No. 09/211,197 filed Dec. 14, 1998, now abandoned.

The present invention relates to a stabilizer mixture containing asterically hindered amine compound and two different Mg- and/orZn-compounds, the use of this mixture for stabilizing an organicmaterial, in particular a polyolefin, against degradation induced bylight, heat or oxidation and the organic material thus stabilized.

The stabilization of polyolefins is described in numerous publications,for example in U.S. Pat. No. 4,929,652, U.S. Pat. No. 5,025,051, U.S.Pat. No. 5,037,870, EP-A-276,923, EP-A-290,388, EP-A-429,731,EP-A-468,923, EP-A-661,341, EP-A-690,094, DE-A-19,545,896 (Derwent96-278,994/29; Chemical Abstracts 125:116779q), WO-A-95/25,767,GB-A-2,293,827 and Chemical Abstracts 106:197407z.

In more detail, the present invention relates to

-   A stabilizer mixture containing-   (A) a sterically hindered amine compound, and-   (B) two different compounds selected from the group consisting of an    organic salt of Zn, an inorganic salt of Zn, Zn-oxide, Zn-hydroxide,    an organic salt of Mg, an inorganic salt of Mg, Mg-oxide and    Mg-hydroxide, the weight ratio of the two different compounds being    1:10 to 10:1;-   With the provisos that    -   (1) the stabilizer mixture is essentially free of perchloric        acid, and    -   (2) the two compounds in component (b) are different from the        combination ZnO and Zn stearate and the combination ZnO and        hydrotalcite.

The weight ratio of the two different compounds of component (B) ispreferably 1:5 to 5:1, in particular 1:2 to 2:1.

The sterically hindered amine is preferably a compound containing atleast one group of the formula (I) or (II)

in which G is hydrogen or methyl, and

-   G₁ and G₂, independently of one another, are hydrogen, methyl or    together are a substituent ═O.

More detailed examples of sterically hindered amines are described belowunder classes (a′) to (i′).

(a′) A compound of the formula (Ia)

in which n₁ is a number from 1 to 4, G and G₁, independently of oneanother, are hydrogen or methyl,

-   G₁₁ is hydrogen, O, hydroxyl, C₁–C₁₈alkyl, C₃–C₈alkenyl,    C₃–C₈alkynyl, C₇–C₁₂aralkyl, C₁–C₁₈alkoxy, C₅–C₈cycloalkoxy,    C₇–C₉phenylalkoxy, C₁–C₈alkanoyl, C₃–C₅alkenoyl, C₁–C₁₈alkanoyloxy,    glycidyl or a group of the formula —CH₂CH(OH)-Z, in which Z is    hydrogen, methyl or phenyl, G₁₁ preferably being H, C₁–C₄alkyl,    allyl, benzyl, acetyl or acryloyl, and-   G₁₂, if n₁ is 1, is hydrogen, C₁–C₁₈alkyl which is uninterrupted or    interrupted by one or more oxygen atoms, cyanoethyl, benzoyl,    glycidyl, a monovalent radical or an aliphatic, cycloaliphatic,    araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid    or phosphorus-containing acid or a monovalent silyl radical,    preferably a radical of an aliphatic carboxylic acid having 2 to 18    carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15    carbon atoms, or an α,β-unsaturated carboxylic acid having 3 to 5    carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon    atoms, where each carboxylic acid can be substituted in the    aliphatic, cycloaliphatic or aromatic moiety by 1 to 3 —COOZ₁₂    groups, in which Z₁₂ is H, C₁–C₂₀alkyl, C₃–C₁₂alkenyl,    C₅–C₇cycloalkyl, phenyl or benzyl,-   G₁₂, if n₁ is 2, is C₂–C₁₂alkylene, C₄–C₁₂alkenylene, xylylene, a    divalent radical of an aliphatic, cycloaliphatic, araliphatic or    aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing    acid or a divalent silyl radical, preferably a radical of an    aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a    cycloaliphatic or aromatic dicarboxylic acid having 8–14 carbon    atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid    having 8–14 carbon atoms, where each dicarboxylic acid may be    substituted in the aliphatic, cycloaliphatic or aromatic moiety by    one or two —COOZ₁₂ groups,-   G₁₂, if n₁ is 3, is a trivalent radical of an aliphatic,    cycloaliphatic or aromatic tricarboxylic acid, which may be    substituted in the aliphatic, cycloaliphatic or aromatic moiety by    —COOZ₁₂, of an aromatic tricarbamic acid or of a    phosphorus-containing acid, or is a trivalent silyl radical,-   and G₁₂, if n₁ is 4, is a tetravalent radical of an aliphatic,    cycloaliphatic or aromatic tetracarboxylic acid.

The carboxylic acid radicals mentioned above are in each case taken tomean radicals of the formula (—CO)_(x)R, where x is as defined above,and the meaning of R arises from the definition given.

Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-hexadecyl or n-octadecyl.

C₃–C₈alkenyl G₁₁ can be, for example, 1-propenyl, allyl, methallyl,2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, or 4-tert-butyl-2-butenyl.

C₃–C₈alkynyl G₁₁ is preferably propargyl.

C₇–C₁₂aralkyl G₁₁ is, in particular, phenethyl, especially benzyl.

C₁–C₁₈alkoxy G₁₁ is, for example, methoxy, ethoxy, propoxy, isopropoxy,butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy,decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.C₆–C₁₂alkoxy, in particular heptoxy and octoxy, is preferred.

C₅–C₈cycloalkoxy G₁₁ is, for example, cyclopentoxy, cyclohexoxy,cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.C₅–C₈cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, ispreferred.

C₇–C₉phenylalkoxy is, for example, benzyloxy.

C₁–C₈alkanoyl G₁₁ is, for example, formyl, propionyl, butyryl, octanoyl,but preferably acetyl and C₃–C₅alkenoyl G₁₁ is in particular acryloyl.

C₁–C₁₈alkanoyloxy G₁₁ is, for example, formyloxy, acetyloxy,propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy andstearoyloxy.

Examples of several G₁₂ radicals are given below.

If G₁₂ is a monovalent radical of a carboxylic acid, it is, for example,an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl orβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

If G₁₂ is a monovalent silyl radical, it is, for example, a radical ofthe formula —(C_(j)H_(2j))—Si(Z′)₂Z″, in which j is an integer in therange from 2 to 5, and Z′ and Z″, independently of one another, areC₁–C₄alkyl or C₁–C₄alkoxy.

If G₁₂ is a divalent radical of a dicarboxylic acid, it is, for example,a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl,itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl,butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl orbicycloheptenedicarbonyl radical or a group of the formula

If G₁₂ is a trivalent radical of a tricarboxylic acid, it is, forexample, a trimellitoyl, citryl or nitrilotriacetyl radical.

If G₁₂ is a tetravalent radical of a tetracarboxylic acid, it is, forexample, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acidor of pyromellitic acid.

If G₁₂ is a divalent radical of a dicarbamic acid, it is, for example,hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.

Preference is given to compounds of the formula (Ia) in which G and G₁are hydrogen, G₁₁ is hydrogen or methyl, n₁ is 2 and G₁₂ is the diacylradical of an aliphatic dicarboxylic acid having 4–12 carbon atoms.

Examples of polyalkylpiperidine compounds from this class are thefollowing compounds:

-   1) 4-hydroxy-2,2,6,6-tetramethylpiperidine-   2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine-   3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine-   4)    1-(4-tert-butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine-   5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine-   6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine-   7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine-   8) 1,2,2,6,6-pentamethylpiperidin-4-yl    β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate-   9) di(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)maleate-   10) di(2,2,6,6-tetramethylpiperidin-4-yl)succinate-   11) di(2,2,6,6-tetramethylpiperidin-4-yl)glutarate-   12) di(2,2,6,6-tetramethylpiperidin-4-yl)adipate-   13) di(2,2,6,6-tetramethylpiperidin-4-yl)sebacate-   14) di(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate-   15) di(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)sebacate-   16) di(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalate-   17) 1-hydroxy-4-β-cyanoethoxy-2,2,6,6-tetramethylpiperidine-   18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate-   19) tri(2,2,6,6-tetramethylpiperidin-4-yl)trimellitate-   20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine-   21) di(2,2,6,6-tetramethylpiperidin-4-yl)diethylmalonate-   22) di(1,2,2,6,6-pentamethylpiperidin-4-yl)dibutylmalonate-   23)    di(1,2,2,6,6-pentamethylpiperidin-4-yl)butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate-   24) di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate-   25) di(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate-   26)    hexane-1′,6′-bis(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine)-   27)    toluene-2′,4′-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine)-   28) dimethylbis(2,2,6,6-tetramethylpiperidin-4-oxy)silane-   29) phenyltris(2,2,6,6-tetramethylpiperidin-4-oxy)silane-   30) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)phosphite-   30-a) tris(1-methyl-2,2,6,6-tetramethylpiperidin-4-yl)phosphite-   31) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)phosphate-   32) phenyl bis(1,2,2,6,6-pentamethylpiperidin-4-yl)phosphonate-   33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine-   34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine-   35) 4-hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine-   36) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine-   36-a)    1,2,3,4-tetrakis[2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl]butane-   36-b)    1,2,3,4-tetrakis[1,2,2,6,6-pentamethylpiperidin-4-yloxycarbonyl]butane-   36-c) 2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl(C₁₅–C₁₇alkane)

(b′) A compound of the formula (Ib)

in which n₂ is the number 1, 2 or 3, G, G₁ and G₁₁ are as defined under(a′),

-   G₁₃ is hydrogen, C₁–C₁₂alkyl, C₂–C₅hydroxyalkyl, C₅–C₇cycloalkyl,    C₇–C₈aralkyl, C₁–C₁₈alkanoyl, C₃–C₅alkenoyl, benzoyl or a group of    the formula

-    and G₁₄, if n₂ is 1, is hydrogen, C₁–C₁₈alkyl, C₃–C₈alkenyl,    C₅–C₇cycloalkyl, C₁–C₄alkyl which is substituted by a hydroxyl,    cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the    formula —CH₂—CH(OH)-Z or of the formula —CONH-Z, in which Z is    hydrogen, methyl or phenyl;-   G₁₄, if n₂ is 2, is C₂–C₁₂alkylene, C₆–C₁₂arylene, xylylene, a    —CH₂—CH(OH)—CH₂ group or a —CH₂—CH(OH)—CH₂—O-D-O— group, in which D    is C₂–C₁₀alkylene, C₆–C₁₅arylene, C₆–C₁₂cycloalkylene, or, provided    that G₁₃ is not alkanoyl, alkenoyl or benzoyl, G₁₄ can alternatively    be 1-oxo-C₂–C₁₂alkylene, a divalent radical of an aliphatic,    cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or    alternatively the group —CO—,-   G₁₄, if n₂ is 3, is a group

-    or, if n₂ is 1, G₁₃ and G₁₄ together can be the divalent radical of    an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic    acid.

Some examples for the radicals G₁₃, G₁₄ and D are given below.

Any alkyl substituents are as defined above for (a′).

Any C₅–C₇cycloalkyl substituents are, in particular, cyclohexyl.

C₇–C₈aralkyl G₁₃ is, in particular, phenylethyl or especially benzyl.

C₂–C₅hydroxyalkyl G₁₃ is, in particular, 2-hydroxyethyl or2-hydroxypropyl.

C₁–C₁₈alkanoyl G₁₃ is, for example, formyl, acetyl, propionyl, butyryl,octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl,and C₃–C₅alkenoyl G₁₃ is, in particular, acryloyl.

C₂–C₈alkenyl G₁₄ is, for example, allyl, methallyl, 2-butenyl,2-pentenyl, 2-hexenyl or 2-octenyl.

G₁₄ as a hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substitutedC₁–C₄alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl,2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl,2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.

Any C₂–C₁₂alkylene radicals are, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene,decamethylene or dodecamethylene.

Any C₆–C₁₅arylene substituents are, for example, o-, m- or p-phenylene,1,4-naphthylene or 4,4′-diphenylene.

C₆–C₁₂cycloalkylene is, in particular, cyclohexylene.

G₁₄ as 1-oxo-C₂–C₁₂alkylene is preferably a group

Preference is given to compounds of the formula (Ib) in which n₂ is 1 or2, G and G₁ are hydrogen, G₁₁ is hydrogen or methyl, G₁₃ is hydrogen,C₁–C₁₂alkyl or a group of the formula

and G₁₄, in the case where n=1, is hydrogen or C₁–C₁₂alkyl, and, in thecase where n=2, is C₂–C₈alkylene or 1-oxo-C₂–C₈alkylene.

Examples of polyalkylpiperidine compounds from this class are thefollowing compounds:

-   37)    N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diamine-   38)    N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diacetamide-   39) bis(2,2,6,6-tetramethylpiperidin-4-yl)amine-   40) 4-benzoylamino-2,2,6,6-tetramethylpiperidine-   41)    N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N′-dibutyladipamide-   42)    N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N′-dicyclohexyl-2-hydroxypropylene-1,3-diamine-   43) N,N′-bis(2,2,6,6-tetramethylpiperidin4-yl)-p-xylylenediamine-   44) N,N′-bis(2,2,6,6-tetramethylpiperidin4-yl)succinamide-   45) bis(2,2,6,6-tetramethylpiperidin-4-yl)    N-(2,2,6,6-tetramethylpiperidin4-yl)-β-aminodipropionate-   46) The compound of the formula

-   47) 4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiperidine-   48)    4-(3-methyl-4-hydroxy-5-tert-butyl-benzamido)-2,2,6,6-tetramethylpiperidine-   49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine

-   49-b)    N,N′,N″-tris[2,2,6,6-tetramethylpiperidin-4-ylamino(2-hydroxypropylene)]isocyanurate-   49-c)    2-(2,2,6,6-tetramethylpiperidin-4-ylamino)-2-(2,2,6,6-tetramethylpiperidin-4-ylaminocarbonyl)propane-   49-d)    1,6-bis[N-(2,2,6,6-tetramethylpiperidin-4-yl)formylamino]hexane

(c′) A compound of the formula (Ic)

in which n₃ is the number 1 or 2, G, G₁ and G₁₁ are as defined under(a′), and G₁₅, if n₃ is 1, is C₂–C₈alkylene, C₂–C₈hydroxyalkylene orC₄–C₂₂acyloxyalkylene, and if n₃ is 2, G₁₅ is the (—CH₂)₂C(CH₂—)₂ group.

C₂–C₈alkylene or C₂–C₈hydroxyalkylene G₁₅ is, for example, ethylene,1-methylethylene, propylene, 2-ethylpropylene or2-ethyl-2-hydroxymethylpropylene.

C₄–C₂₂acyloxyalkylene G₁₅ is, for example,2-ethyl-2-acetoxymethylpropylene.

Examples of polyalkylpiperidine compounds from this class are thefollowing compounds:

-   50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane-   51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane-   52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane-   53)    9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]undecane-   54)    9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]-undecane-   55)    2,2,6,6-tetramethylpiperidine-4-spiro-2′-(1′,3′-dioxane)-5′-spiro-5″-(1″,3″-dioxane)-2″-spiro-4′″-(2′″,2′″,6′″,6′″-tetramethylpiperidine)

(d′) A compound of the formula (Id-1), (Id-2) or (Id-3),

in which n₄ is the number 1 or 2, G, G₁ and G₁₁ are as defined under(a′), G₁₆ is hydrogen, C₁–C₁₂alkyl, allyl, benzyl, glycidyl orC₂–C₆alkoxyalkyl, and G₁₇, if n₄ is 1, is hydrogen, C₁–C₁₂alkyl,C₃–C₅alkenyl, C₇–C₉aralkyl, C₅–C₇cycloalkyl, C₂–C₄hydroxyalkyl,C₂–C₆alkoxyalkyl, C₆–C₁₀aryl, glycidyl or a group of the formula—(CH₂)_(p)—COO-Q or —(CH₂)_(p)—O—CO-Q, in which p is 1 or 2, and Q isC₁–C₄alkyl or phenyl, and G₁₇, if n is 2, is C₂–C₁₂alkylene,C₄–C₁₂alkenylene, C₆–C₁₂arylene, a group of the formula—CH₂—CH(OH)—CH₂—O-D′-O—CH₂—CH(OH)—CH₂—, in which D′ is C₂–C₁₀alkylene,C₆–C₁₅arylene, C₆–C₁₂cycloalkylene or a group of the formula—CH₂CH(OD″)CH₂—(OCH₂—CH(OD″)CH₂)₂—, in which D″ is hydrogen,C₁–C₁₈alkyl, allyl, benzyl, C₂–C₁₂alkanoyl or benzoyl, T₁ and T₂,independently of one another, are hydrogen, C₁–C₁₈alkyl or unsubstitutedor halogen- or C₁–C₄alkyl-substituted C₆–C₁₀aryl or C₇–C₉aralkyl, or T₁and T₂ together with the carbon atom bonding them form aC₅–C₁₄cycloalkane ring.

A compound of the formula (Id-3) is preferred.

Some examples of the several variables in the formulae (Id-1), (Id-2)and (Id-3) are given below.

Any C₁–C₁₂alkyl substituents are, for example, methyl, ethyl, n-propyl,n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl,n-decyl, n-undecyl or n-dodecyl.

Any C₁–C₁₈alkyl substituents can be, for example, the abovementionedgroups and in addition, for example, n-tridecyl, n-tetradecyl,n-hexadecyl or n-octadecyl.

Any C₂–C₆alkoxyalkyl substituents are, for example, methoxymethyl,ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl,ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl orpropoxypropyl.

C₃–C₅alkenyl G₁₇ is, for example, 1-propenyl, allyl, methallyl,2-butenyl or 2-pentenyl.

C₇–C₉aralkyl G₁₇, T₁ and T₂ are, in particular, phenethyl or especiallybenzyl. If T₁ and T₂ together with the carbon atom form a cycloalkanering, this can be, for example, a cyclopentane, cyclohexane, cyclooctaneor cyclododecane ring.

C₂–C₄hydroxyalkyl G₁₇ is, for example, 2-hydroxyethyl, 2-hydroxypropyl,2-hydroxybutyl or 4-hydroxybutyl.

C₆–C₁₀aryl G₁₇, T₁ and T₂ are, in particular, phenyl or α- orβ-naphthyl, which are unsubstituted or substituted by halogen orC₁–C₄alkyl.

C₂–C₁₂alkylene G₁₇ is, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene,decamethylene or dodecamethylene.

C₄–C₁₂alkenylene G₁₇ is, in particular, 2-butenylene, 2-pentenylene or3-hexenylene.

C₆–C₁₂arylene G₁₇ is, for example, o-, m- or p-phenylene,1,4-naphthylene or 4,4′-diphenylene.

C₂–C₁₂alkanoyl D″ is, for example, propionyl, butyryl, octanoyl,dodecanoyl, but preferably acetyl.

C₂–C₁₀alkylene, C₆–C₁₅arylene or C₆–C₁₂cycloalkylene D′ have, forexample, one of the definitions given for D under (b′).

Examples of polyalkylpiperidine compounds from this class are thefollowing compounds:

-   56)    3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione-   57)    3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione-   58)    3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione-   59)    3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione-   60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione-   61)    2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane-   62)    2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane-   63)    2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane-   64)    2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]decane    and preferably:-   65)    8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione    and the compounds of the following formulae:

-   69-b) Mixture of 60% by weight of

-    and 40% by weight of

-   (e′) A compound of the formula (Ie)

-   in which n₅ is the number 1 or 2, and G₁₈ is a group of the formula

-   in which G and G₁₁ are as defined under (a′), and G₁ and G₂ are    hydrogen, methyl or, together, are a substituent ═O,-   E is —O— or —ND′″-,-   A is C₂–C₆alkylene or —(CH₂)₃—O— and-   x₁ is the number 0 or 1,-   D′″ is hydrogen, C₁–C₁₂alkyl, C₂–C₅hydroxyalkyl or C₅–C₇cycloalkyl,-   G₁₉ is identical to G₁₈ or is one of the groups —N(G₂₁)(G₂₂), —OG₂₃,    —N(H)(CH₂OG₂₃) or —N(CH₂OG₂₃)₂,-   G₂₀, if n=1, is identical to G₁₈ or G₁₉ and, if n=2, is an    -E-D^(IV)-E-group, in which D^(IV) is C₂–C₈alkylene or C₂–C₈alkylene    which is interrupted by 1 or 2-NG₂₁-groups,-   G₂₁ is C₁–C₁₂alkyl, cyclohexyl, benzyl or C₁–C₄-hydroxyalkyl or a    group of the formula

-    G₂₂ is C₁–C₁₂alkyl, cyclohexyl, benzyl or C₁–C₄hydroxyalkyl, and-   G₂₃ is hydrogen, C₁–C₁₂alkyl or phenyl, or G₂₁ and G₂₂ together are    C₄–C₅alkylene or C₄–C₅oxaalkylene, for example —CH₂CH₂—O—CH₂CH₂—, or    a group of the formula —CH₂CH₂—N(G₁₁)—CH₂CH₂—.

Some examples of the several variables in the formula (Ie) are givenbelow.

Any C₁–C₁₂alkyl substituents are, for example, methyl, ethyl, n-propyl,n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl,n-decyl, n-undecyl or n-dodecyl.

Any hydroxyalkyl substituents are, for example, 2-hydroxyethyl,2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

Any C₅–C₇cycloalkyl substituents are, for example, cyclopentyl,cyclohexyl or cycloheptyl. Cyclohexyl is preferred.

C₂–C₆alkylene A is, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene or hexamethylene.

If G₂₁ and G₂₂ together are C₄–C₅alkylene or oxaalkylene, they are, forexample, tetramethylene, pentamethylene or 3-oxapentamethylene.

Examples of polyalkylpiperidine compounds from this class are thecompounds of the following formulae:

where R is

where R has the same meaning as in compound 74.

where R′ is

where R′ has the same meaning as in compound 76.

(f′) A compound of the Formula (If)

wherein G₁₁ is as defined under (a′).

A preferred example from this class is the following compound:

(g′) Oligomeric or polymeric compounds whose recurring structural unitcontains a 2,2,6,6-tetraalkylpiperidinyl radical, in particularpolyesters, polyethers, polyamides, polyamines, polyurethanes,polyureas, polyaminotriazines, poly(meth)acrylates,poly(meth)acrylamides and copolymers thereof which contain suchradicals.

Examples of 2,2,6,6-polyalkylpiperidine compounds from this class arethe compounds of the following formulae, where m₁ to m₁₄ is a numberfrom 2 to about 200, preferably 2 to 100, for example 2 to 50,2 to 40 or3 to 40 or 4 to 10.

The meanings of the end groups which saturate the free valences in theoligomeric or polymeric compounds listed below depend on the processesused for the preparation of said compounds. The end groups can also inaddition be modified after the synthesis of the compounds.

In the compounds 81 and 82, the end group bonded to the —O— can be, forexample, hydrogen or a group —CO—(CH₂)₂—COO—Y or —CO—(CH₂)₄—COO—Y,respectively, with Y being hydrogen or C₁–C₄alkyl and the end groupbonded to the diacyl can be, for example, —O—Y or a group

In the compound 83, the end group bonded to the amino residue can be,for example, a group

and the end group bonded to the diacyl residue can be, for example, Cl.

In the compounds 84-1 and 84-2, the end group bonded to the triazineresidue can be, for example, chlorine or a group

and the end group bonded to the diamino group can be, for example,hydrogen or a group

It may be convenient to replace the chlorine attached to the triazine bye.g. —OH or an amino group. Suitable amino groups are typically:pyrrolidin-1-yl, morpholino, —NH₂, —N(C₁–C₈alkyl)₂ and —NY′(C₁–C₈alkyl)wherein Y′ is hydrogen or a group of the formula

In the compound 85, the end group bonded to the2,2,6,6-tetramethylpiperidin-4-ylamino residue can be, for example,hydrogen and the end group bonded to the 2-hydroxypropylene residue canbe, for example,

In the compound 86, the end group bonded to the —O— can be, for example,hydrogen or

and the end group bonded to the diacyl residue can be, for example,—OCH₃ or Cl.

In the compound 87, the end group bonded to the —O— can be, for example,hydrogen or

and the end group bonded to the diacyl radical can be, for example,—OCH₃ or Cl.

In the compound 88, the end group bonded to the —O— can be, for example,hydrogen or

and the end group bonded to the diacyl radical can be, for example,—OCH₃ or Cl.

In the compound 89, the end group bonded to the —CH₂— can be, forexample, hydrogen and the end group bonded to the ester residue can be,for example,

In the compound 90, the end group bonded to the —CH₂— can be, forexample, hydrogen and the end group bonded to the ester residue can be,for example,

In the compound 91, the end group bonded to the —CH₂— can be, forexample, hydrogen and the end group bonded to the amide residue can be,for example,

In the compound 92, the end group bonded to the triazine residue can be,for example, chlorine or a group

and the end group bonded to the diamino residue can be, for example,hydrogen or a group

It may be convenient to replace the chlorine attached to the triazine bye.g. —OH or an amino group. Suitable amino groups are typically:pyrrolidin-1-yl, morpholino, —NH₂, —N(C₁–C₈alkyl)₂ and —NY′(C₁–C₈alkyl)wherein Y′ is hydrogen or a group of the formula

Preferred is also a compound which corresponds to compound 92 whereinthe 2,2,6,6-tetramethyl-4-piperidyl groups are replaced by1,2,2,6,6-pentamethyl-4-piperidyl groups.

In the compound 93, the end group bonded to the diamino residue can be,for example, hydrogen and the end group bonded to the —CH₂CH₂— residuecan be, for example,

In the compound 94, the end group bonded to the diamino residue can be,for example, hydrogen and the end group bonded to the diacyl residue canbe, for example, Cl.

in which R″ is a group of the formula

or the chain branching

-   R′″ is a group of the formula (95-I), and-   m′₁₅ and m″₁₅ are each a number from 0 to 200, preferably 0 to 100,    in particular 0 to 50, with the proviso that m′₁₅+m″₁₅ is a number    from 2 to 200, preferably 2 to 100, in particular 2 to 50. In the    compound 95, the end group bonded to the diamino residue can be, for    example, hydrogen and the end group bonded to the —CH₂CH₂— group can    be, for example, halogen, in particular Cl or Br.

Further examples for polymeric compounds are:

1) A compound of the formula (96-I) or (96-II)

wherein m₁₆ and m₁₆* are a number from 2 to 50, for example 2 to 25.

During the preparation, the compounds of the formulae (96-I) and (96-II)can be obtained together as a mixture and therefore, can also beemployed as such. The (96-I):(96-II) weight ratio is, for example, from20:1 to 1:20 or from 1:10 to 10:1.

In the compounds of the formula (96-I), the terminal group bonded to thenitrogen can be, for example, hydrogen and the terminal group bonded tothe 2-hydroxypropylene radical can be, for example, a

group.

In the compounds of the formula (96-II), the terminal group bonded tothe dimethylene radical can be, for example, —OH, and the terminal groupbonded to the oxygen can be, for example, hydrogen. The terminal groupscan also be polyether radicals.

2) A compound of the formula (97)

wherein G₂₄, G₂₅, G₂₆, G₂₇ and G₂₈, independently of one another, are adirect bond or C₁–C₁₀alkylene, G₁₁ is as defined under (a′) and m₁₇ is anumber from 1 to 50, for example 2 to 25.

In the compound of the formula (97), the end group bonded to the >C═Ogroup can be, for example,

and the end group bonded to the oxygen can be, for example

Preferred are the following two compounds:

wherein the mean value of m₁₇ is 2.5.

3) A compound of the formula (98)

in which approximately one third of the radicals R^(IV) are —C₂H₅ andthe others are a group

and m₁₈ is a number in the range from 2 to 200, preferably 2 to 100, inparticular 2 to 50.

In the compound (98), the end group bonded to the —CH₂— residue can be,for example, hydrogen and the end group bonded to the —CH(CO₂R^(IV))—residue can be, for example, —CH═CH—COOR^(IV).

4) A compound of the formula (99)

in which G₁₁ is as defined under (a′), G₂₉ and G₃₂, independently of oneanother, are a direct bond or a —N(X₁)—CO—X₂—CO—N(X₃)— group, where X₁and X₃, independently of one another, are hydrogen, C₁–C₈alkyl,C₅–C₁₂cycloalkyl, phenyl, C₇–C₉phenylalkyl or a group of the formula(99-1)

and X₂ is a direct bond or C₁–C₄alkylene, G₃₀, G₃₁, G₃₄ and G₃₅,independently of one another, are hydrogen, C₁–C₃₀alkyl,C₅–C₁₂cycloalkyl or phenyl, G₃₃ is hydrogen, C₁–C₃₀alkyl,C₅–C₁₂cycloalkyl, C₇–C₉phenylalkyl, phenyl or a group of the formula(99-1), and m₁₉ is a number from 1 to 50.

In the compounds of the formula (99), the end group bonded to the2,5-dioxopyrrolidine ring can be, for example, hydrogen, and the endgroup bonded to the —C(G₃₄)(G₃₅)-radical can be, for example,

Examples of the compounds of the formula (99) are:

wherein G₁₁ is hydrogen or methyl, and m₁₉ is a number from 1 to 25.

5) A product obtainable by reacting an intermediate product, obtained byreaction of a polyamine of the formula (100a) with cyanuric chloride,with a compound of the formula (100b)

in which m′₂₀, m″₂₀ and m′″₂₀, independently of one another, are anumber from 2 to 12, G₃₆ is hydrogen, C₁–C₁₂alkyl, C₅–C₁₂cycloalkyl,phenyl or C₇–C₉phenylalkyl, and G₁₁ is as defined under (a′). Apreferred product has the Chemical Abstracts-CAS No. 136 504-96-6(Compound 100-A).

In general, the above reaction product can be represented for example bya compound of the formula 100-1, 100-2 or 100-3. It can also be in theform of a mixture of these three compounds.

A preferred meaning of the formula (100-1) is

A preferred meaning of the formula (100-2) is

A preferred meaning of the formula (100-3) is

In the above formulae 100-1 to 100-3, m₂₀ is preferably 1 to 20.

6) A compound of the formula (101)

in which G₁₁ is as defined under (a′), G₃₇ is C₁–C₁₀alkyl,C₅–C₁₂cycloalkyl, C₁–C₄alkyl-substituted C₅–C₁₂cycloalkyl, phenyl orC₁–C₁₀alkyl-substituted phenyl, G₃₈ is C₃–C₁₀alkylene and m₂₁ is anumber from 1 to 50, for example 2 to 25.

In the compounds of the formula (101), the terminal group bonded to thesilicon atom can be, for example, (G₃₇)₃Si—O—, and the terminal groupbonded to the oxygen can be, for example, —Si(G₃₇)₃.

The compounds of the formula (101) can also be in the form of cycliccompounds if m₂₁ is a number from 3 to 10, i.e. the free valences shownin the structural formula then form a direct bond.

An example of a compound of the formula (101) is

with m₂₁ being a number from 1 to 20.

In the above shown oligomeric and polymeric compounds,

-   examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl,    sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl,    1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,    isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl,    n-octyl, 2-ethyl-hexyl, 1,1,3-trimethylhexyl,    1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl,    dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl,    pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl and docosyl;-   examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and    cyclooctyl; an example of C₇–C₉phenylalkyl is benzyl; and-   examples of alkylene are ethylene, propylene, trimethylene,    tetramethylene, pentamethylene, 2,2-dimethyltrimethylene,    hexamethylene, trimethylhexamethylene, octamethylene and    decamethylene.

(h′) A compound of the formula (Ih)

in which n₆ is the number 1 or 2, G and G₁₁ are as defined under (a′),and G₁₄ is as defined under (b′), but G₁₄ cannot be —CONH-Z and—CH₂—CH(OH)—CH₂—O-D-O—.

Examples of such compounds are the following:

(i′) A compound of the formula (Ii)

wherein the radicals G₃₉, independently of one another, are a group ofthe formula (Ii-1)

in which G₄₀ is C₁–C₁₂alkyl or C₅–C₁₂cycloalkyl, G₄₁ is C₂–C₁₂alkyleneand G₄₂ is hydrogen, C₁–C₈alkyl, —O, —CH₂CN, C₃–C₆alkenyl,C₇–C₉phenylalkyl, C₇–C₉phenylalkyl which is substituted on the phenylradical by C₁–C₄alkyl; or C₁–C₈acyl.

Alkyl is for example C₁–C₄alkyl, in particular methyl, ethyl, propyl orbutyl.

Cycloalkyl is preferably cyclohexyl.

Alkylene is for example ethylene, propylene, trimethylene,tetramethylene, pentamethylene, 2,2-dimethyltrimethylene orhexamethylene.

Alkenyl is preferably allyl.

Phenylalkyl is preferably benzyl.

Acyl is preferably acetyl.

Examples of compounds from this class are the compounds of the followingformulae:

The sterically hindered amine (component (A)) is preferably one of theabove compounds 1 to 106. The compounds 5, 10, 13, 14, 24, 25, 36-a,36-b, 49-a-I, 49-a-II, 49-e, 63, 75, 76, 80-a, 81, 84-1, 84-2, 92, 93,96-I, 96-II, 97-I, 97-II, 99-I, 100-A, 101-I, 105 and 106 are ofinterest. The compounds 5, 10, 13, 14, 36-a, 36-b, 36-d, 49-a-I,49-a-II, 49-d, 49-e, 63, 69-a, 76, 80-a, 81, 84-1, 84-2, 92, 96-I,96-II, 97-II, 99-I, 99-II, 99-III, 100-A, 101-I and 105 are preferredand the compounds 13, 14, 36-a, 36-b, 49-a-I, 49-a-II, 63, 76, 81, 84-1,92, 96-I, 96-II, 100-A and 101-I are particularly preferred.

The organic salt of zinc or magnesium defined in component (B) ispreferably a compound of the formula MeL₂ in which Me is zinc ormagnesium and L is an anion of an organic acid or of an enol. Theorganic acid can, for example, be a sulfonic acid, sulfinic acid,phosphonic acid or phosphinic acid, but is preferably a carboxylic acid.The acid can be aliphatic, aromatic, araliphatic or cycloaliphatic; itcan be linear or branched; it can be substituted by hydroxyl or alkoxygroups; it can be saturated or unsaturated and it preferably contains 1to 24 carbon atoms.

Examples of carboxylic acids of this type are formic, acetic, propionic,butyric, isobutyric, caprioic, 2-ethylcaproic, caprylic, capric, lauric,palmitic, stearic, behenic, oleic, lactic, ricinoleic,2-ethoxypropionic, benzoic, salicylic, 4-butylbenzoic, toluic,4-dodecylbenzoic, phenylacetic, naphthylacetic, cyclohexanecarboxylic,4-butylcyclohexanecarboxylic or cyclohexylacetic acid. The carboxylicacid can also be a technical mixture of carboxylic acids, for exampletechnical mixtures of fatty acids or mixtures of alkylated benzoicacids.

Examples of organic acids containing sulfur or phosphorus aremethanesulfonic, ethanesulfonic, α,α-dimethylethanesulfonic,n-butanesulfonic, n-dodecanesulfonic, benzenesulfonic, toluenesulfonic,4-nonylbenzenesulfonic, 4-dodecylbenzenesulfonic or cyclohexanesulfonicacid, dodecanesulfinic, benzenesulfinic or naphthalenesulfinic acid,butylphosphonic acid, phenylphosphonic acid, monomethyl or monoethylphenylphosphonate, monobutyl benzylphosphonate, dibutylphosphinic acidor diphenylphosphinic acid.

If L is an enolate anion, it is preferably an anion of a β-dicarbonylcompound or of an o-acylphenol. Examples of β-dicarbonyl compounds areacetylacetone, benzoylacetone, dibenzoylmethane, ethyl acetoacetate,butyl acetoacetate, lauryl acetoacetate or α-acetylcyclohexanone.Examples of o-acylphenols are 2-acetylphenol, 2-butyroylphenol,2-acetyl-1-naphthol, 2-benzoylphenol or salicylaldehyde. The enolate ispreferably the anion of a β-dicarbonyl compound having 5 to 20 carbonatoms.

Organic salts of zinc or magnesium are preferably an acetylacetonate oran aliphatic monocarboxylate having, for example, 1 to 24 carbon atoms.Magnesium acetate, laurate and stearate, zinc formate, acetate,oenanthate, laurate and stearate as well as zinc acetylacetonate andmagnesium acetylacetonate are some of the particular preferred examples.

Zinc stearate, magnesium stearate, zinc acetylacetonate, magnesiumacetylacetonate, zinc acetate and magnesium acetate are of specialinterest.

The inorganic compound of zinc or magnesium is for example Zinc oxide,magnesium oxide, zinc hydroxide, magnesium hydroxide, or

A carbonate containing comound such as

-   -   Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, dolomite, e.g a        Ca/Mg carbonate such as ®Microdol Super from ®Micro Minerals; or    -   A natural or synthetic hydrotalcite.

The natural hydrotalcite is held to possess a structureMg₆Al₂(OH)₁₆CO₃.4H₂O.

A typical empirical formula of a synthetic hydrotalcite isAl₂Mg_(4.35)OH_(11.36)CO_(3(1.67)).x H₂O.

Examples of the synthetic product include:Mg_(0.7)Al_(0.3)(OH)₂(CO₃)_(0.15).0.54H₂O,Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂O, orMg_(4.2)Al(OH)_(12.4)CO₃.

Preferred synthetic hydrotalcites are L-55R®II from ®REHEIS as well as®ZHT-4A and ®DHT-4A from ®Kyowa Chemical Industry Co.

The two different compounds of component (B), which are present in aweight ratio of 1:10 to 10:1 are for example:

-   Mg-stearate and hydrotalcite (®DHT-4A),-   Zn-stearate and hydrotalcite (®DHT-4A),-   Mg-acetylacetonate and hydrotalcite (®DHT-4A),-   Mg-oxide and hydrotalcite (®DHT-4A),-   Mg-hydroxide and hydrotalcite (®DHT-4A),-   Zn-hydroxide-carbonate and Mg-stearate,-   Zn-hydroxide-carbonate and Zn-stearate,-   Zn-hydroxide-carbonate and Mg-acetylacetonate,-   Zn-hydroxide-carbonate and Mg-oxide,-   Zn-hydroxide-carbonate and Zn-oxide,-   Zn-hydroxide-carbonate and Mg-hydroxide,-   hydrotalcite (®REHEIS) and Mg-stearate,-   hydrotalcite (®REHEIS) and Zn-stearate,-   hydrotalcite (®REHEIS) and Mg-oxide,-   dolomite (®Microdol Super) and Zn-stearate,-   dolomite (®Microdol Super) and Mg-stearate,-   dolomite (®Microdol Super) and Zn-oxide,-   dolomite (®Microdol Super) and Mg-hydroxide,-   Mg-stearate and Zn-stearate,-   Mg-stearate and Zn-acetylacetonate,-   Mg-stearate and Mg-oxide,-   Mg-stearate and Zn-oxide,-   Mg-stearate and Mg-hydroxide,-   Zn-stearate and Mg-acetate,-   Zn-stearate and Mg-oxide,-   Zn-stearate and Mg-hydroxide,-   Mg-acetylacetonate and Zn-acetylacetonate,-   Mg-acetylacetonate and Mg-oxide,-   Mg-acetylacetonate and Zn-oxide,-   Mg-acetylacetonate and Mg-hydroxide,-   Zn-acetylacetonate and Mg-oxide,-   Zn-acetylacetonate and Zn-oxide, or-   Mg-oxide and Zn-oxide.

A preferred embodiment of this invention relates to a stabilizer mixturewherein the two different compounds of component (B) are selected fromthe group consisting of hydrotalcite, dolomite, Zn-hydroxide-carbonate,Mg-hydroxide-carbonate, Zn-oxide, Mg-oxide, Zn-hydroxide, Mg-hydroxide,Zn-stearate, Mg-stearate, Zn-acetylacetonate, Mg-acetylacetonate,Zn-acetate and Mg-acetate.

According to a particular preferred embodiment component (B) does notcontain Zn-oxide.

A stabilizer mixture wherein the two different compounds in component(B) are

-   Mg-stearate and hydrotalcite,-   Zn-stearate and hydrotalcite,-   Mg-stearate and Zn-stearate,-   Zn-stearate and Mg-oxide, or-   Mg-stearate and Mg-hydroxide    is also preferred.

A further preferred embodiment of this invention relates to a stabilizermixture containing additionally

-   (C1) a pigment or-   (C2) an UV absorber or-   (C3) a pigment and an UV absorber.

The pigment (component (C1)) may be an inorganic or organic pigment.

Examples of inorganic pigments are titanium dioxide, zinc oxide, carbonblack, cadmium sulfide, cadmium selenide, chromium oxide, iron oxide,lead oxide and so on.

Examples of organic pigments are azo pigments, anthraquinones,phthalocyanines, tetrachloroisoindolinones, quinacridones, isoindolines,perylenes, pyrrolopyrroles (such as Pigment Red 254) and so on.

All pigments described in “Gächter/Müller: Plastics Additives Handbook,3rd Edition, Hanser Publishers, Munich Vienna New York”, page 647 to659, point 11.2.1.1 to 11.2.4.2 can be used as component (C1).

A particularly preferred pigment is titanium dioxide, optionally incombination with an organic pigment.

Examples of such organic pigments are:

C.I. (Colour Index) Pigment Yellow 93, C.I. Pigment Yellow 95, C.I.Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 155,C.I. Pigment Yellow 162, C.I. Pigment Yellow 168, C.I. Pigment Yellow180, C.I. Pigment Yellow 183, C.I. Pigment Red 44, C.I. Pigment Red 170,C.I. Pigment Red 202, C.I. Pigment Red 214, C.I. Pigment Red 254, C.I.Pigment Red 264, C.I. Pigment Red 272, C.I. Pigment Red 48:2, C.I.Pigment Red 48:3, C.I. Pigment Red 53:1, C.I. Pigment Red 57:1, C.I.Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:3 and C.I.Pigment Violet 19.

Examples of the UV absorber (component (C2)) are a2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone, an ester ofsubstituted or unsubstituted benzoic acid, an acrylate, an oxamide, a2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of resorcinol or aformamidine.

The 2-(2′-hydroxyphenyl)benzotriazole is e.g.2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,mixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]or the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO(CH₂)₃—]₂ whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl.

2-(3′,5′-Di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole and2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)-benzotriazole are preferred.

The 2-hydroxybenzophenone is for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy or2′-hydroxy-4,4′-dimethoxy derivatives.

2-Hydroxy-4-octyloxybenzophenone is preferred.

The ester of a substituted or unsubstituted benzoic acid is for example4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tertbutylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate or 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate andhexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate are preferred.

The acrylate is for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate orN—(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

The oxamide is for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide or its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide or mixtures of ortho- andpara-methoxy-disubstituted oxanilides or mixtures of o- andp-ethoxy-disubstituted oxanilides.

The 2-(2-hydroxyphenyl)-1,3,5-triazine is for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazineor 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine arepreferred.

The monobenzoate of resorcinol is for example the compound of theformula

The formamidine is for example the compound of the formula

The UV absorber is in particular a

2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone or ahydroxyphenyltriazine.

A further preferred embodiment of this invention relates to a stabilizermixture containing additionally an organic salt of Ca or an inorganiccompound of Ca.

Examples of an organic salt of Ca are Ca-stearate, Ca-laurate,Ca-lactate and Ca-stearoyl-lactate.

Examples of an inorganic compound of Ca are CaO and Ca(OH)2

The stabilizer mixture according to this invention is suitable forstabilizing organic materials against degradation induced by light, heator oxidation. Examples of such organic materials are the following:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityand high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EM), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅–C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmeth-acrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as, wellas their copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also poly-esters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

This invention therefore additionally relates to a compositioncomprising an organic material subject to degradation induced by light,heat or oxidation and the stabilizer mixture described above; with theproviso that the organic material is essentially free of perchloricacid.

A further embodiment of the present invention is a method forstabilizing an organic material against degradation induced by light,heat or oxidation, which comprises incorporating into the organicmaterial the stabilizer mixture described above; with the proviso thatthe organic material is essentially free of perchloric acid.

The organic material is preferably a synthetic polymer, in particularfrom one of the above groups. Polyolefins are preferred andpolyethylene, polypropylene and copolymers thereof are particularlypreferred.

The components (A), (B) and optionally (C1) and/or (C2) may be added tothe organic material to be stabilized either individually or mixed withone another.

The sterically hindered amine compound (component (A)) is present in theorganic material in an amount of preferably 0.01 to 5%, in particular0.01 to 1% or 0.05 to 1%, relative to the weight of the organicmaterial.

The two different Mg and/or Zn salts (component (B)), together, arepresent in the organic material in an amount of preferably 0.005 to 1%,in particular 0.05 to 0.2%, relative to the weight of the organicmaterial.

The pigment (component (C1)) is optionally present in the organicmaterial in an amount of preferably 0.01 to 10%, in particular 0.05 to1%, relative to the weight of the organic material.

The UV absorber (component (C2)) is optionally present in the organicmaterial in an amount of preferably 0.01 to 1%, in particular 0.05 to0.5%, relative to the weight of the organic material.

The total amount of component (C3) (the pigment in combination with theUV absorber) is preferably 0.01 to 10%, relative to the weight of theorganic material. The weight ratio of the UV absorber to the pigment isfor example 2:1 to 1:10.

When the pigment used is titanium dioxide in combination with an organicpigment as described above, titanium dioxide is preferably present inthe organic material in an amount of 0.01 to 5%, relative to the weightof the organic material, and the organic pigment may be present in anamount of, for example, 0.01 to 2%, relative to the weight of theorganic material.

The weight ratio of the components (A):(B) is preferably 10:1 to 1:10.

The weight ratio of the components (A):(C1) is preferably 10:1 to 1:10.

The weight ratio of the components (A):(C2) is preferably 20:1 to 1:2.

The weight ratio of the components (A):(C3) is preferably 10:1 to 1:10.

The above components can be incorporated into the organic material to bestabilized by known methods, for example before or during shaping or byapplying the dissolved or dispersed compounds to the organic material,if necessary with subsequent evaporation of the solvent. The componentscan be added to the organic material in the form of a powder, granulesor a masterbatch, which contains these components in, for example, aconcentration of from 2.5 to 25% by weight.

If desired, the components (A), (B) and optionally (C1) and/or (C2) canbe melt blended with each other before incorporation in the organicmaterial. They can be added to a polymer before or during thepolymerization or before the crosslinking.

The materials stabilized according to this invention can be used in awide variety of forms, for example as films, fibres, tapes, mouldingcompositions, profiles or as binders for paints, adhesives or putties.

The stabilized material may additionally also contain variousconventional additives, for example:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butyl-phenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyl-heptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy-phenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexyl-phenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)₄-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxy-phenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5di-tert-butyl4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzyl-phosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3.5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol,4-oc-tadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethyl-aminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, Bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyidiphenylamines, a mixture of mono- anddialkylated nonyidiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylated isopropylisohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines,2,3-di-hydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixtureof mono- und dialkylated tert-butyl/tert-octylphenothiazines, a mixtureof mono- und dialkylated tert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diamino-but-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetra-methylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)-oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methyl-phenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or tinpyrocatecholate.

10. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (“ionomers”).

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

12. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

13. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312,U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643, DE-A-4316611,DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

Particularly preferred conventional additives are those listed aboveunder items 1 and/or 4.

Also the compound of the formula

is one of the preferred conventional additives which may additionally beincorporated into the organic material to be stabilized.

The weight ratio of the total amount of components (A), (B) andoptionally (C1) and/or (C2) to the total amount of the conventionaladditives can be, for example, 100:1 to 1:100.

The examples below illustrate the invention in greater detail. Allpercentages and parts are by weight, unless stated otherwise.

Sterically Hindered Amine Compounds Used in the Following Examples I toVII:

(For the polymeric compounds, the mean degree of polymerization isindicated in each case.)

Mixture of the compounds 96-I and 96-II:

-   (Preferably ®Hostavin N30)

with m₁₆ being 3.9 and m₁₆* being 4.2 and the weight ratio of (96-I) to(96-II) being 4:1.

with m₁₉ being a number from 1 to 25.

Compound 100-A:

-   (®Uvasorb HA88 (Chemical Abstracts CAS No. 136 504-96-6))-   A product obtainable by reacting an intermediate product, obtained    by reaction of a polyamine of the formula (100a-I) with cyanuric    chloride, with a compound of the formula (100b-I).

EXAMPLE I Light Stabilization of Injection Molded 2 mm PolypropylenePlaques

100 parts of polypropylene powder (melt flow index: 2.4 g/10 min at 230°C. and 2160 g) are blended in a barrel mixer with 0.05 parts ofpentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.05 parts oftris[2,4-di-tert-butylphenyl] phosphite, and the stabilizer systemindicated in Tables 1 to 4. Then, the blend is compounded in an extruderat temperatures of 200 °–220° C. The granules obtained on extrusion andgranulation are transformed into 2 mm thick plaques at 240 °–260° C. inan automatic injection molding machine.

The plaques are mounted on sample holders and subjected to naturalweathering in Florida (45° South, direct, approximately 140 kLy/year).Periodically, the carbonyl content of the samples is measured with aninfrared spectrophotometer. The exposure time corresponding to formationof a carbonyl absorbance of, for example, 0.5 (T_(0.5)) is a measure forthe efficiency of the stabilizer system.

The values obtained are summarized in Tables 1 to 4.

The synergistic effect of the two coadditivs ((1) and (2)) is determinedby a comparison of the calculated T_(0.5) value with the actuallymeasured T_(0.5) value. The T_(0.5) values are calculated on the basisof the additivity law (B. Ranby and J. F. Rabek; Photodegradation,Photo-oxidation and Photostabilization of Polymers, Principles andApplications, John Wiley & Sons, London, New York, Sydney, Toronto,1975, pages 418 and 419) according to the following equation:

$\begin{matrix}{Expected} \\{stabilizing} \\{activity}\end{matrix} = \frac{\begin{matrix}{{{Stabilizing}\mspace{14mu}{activity}\mspace{14mu}{of}\mspace{14mu} 100\%\mspace{14mu}(1)} +} \\{{stabilizing}\mspace{14mu}{activity}\mspace{14mu}{of}\mspace{14mu} 100\%\mspace{20mu}(2)}\end{matrix}}{2}$

There is a synergistic effect for the two coadditivs in question, whenT_(0.5measured)>T_(0.5calculated).

TABLE 1 Sterically hindered amine compound: 0.1% of the compound 81T_(0.5 measured) T_(0.5 calculated) Coadditiv (kLy) (kLy) 0.1% ofhydrotalcite (® DHT-4A) 67 0.1% of Mg-hydroxide-carbonate 57 0.1% ofZn-hydroxide-carbonate 81 0.1% of Mg-stearate 71 0.1% of Zn-stearate 720.1% of Mg-acetylacetonate 53 0.1% of Mg-oxide 94 0.1% of Zn-Oxide 730.1% of Mg-hydroxide 60 0.1% of hydrotalcite (® REHEIS) 66 0.1% ofdolomite (® Microdol Super) 53 0.05% of Mg-stearate + 0.05% 85 69 ofhydrotalcite (® DHT-4A) 0.05% of Zn-stearate + 0.05% 86 69.5 ofhydrotalcite (® DHT-4A) 0.05% of Mg-acetylacetonate + 0.05% 92 60 ofhydrotalcite (® DHT-4A) 0.05% of Zn-hydroxide-carbonate + 0.05% 100 77.5of Mg-stearate 0.05% of Zn-hydroxide-carbonate + 0.05% 124 76.5 ofZn-stearate 0.05% of Zn-hydroxide-carbonate + 0.05% 106 67.5 ofMg-acetylacetonate 0.05% of Zn-hydroxide-carbonate + 0.05% 111 87.5 ofMg-oxide 0.05% of Zn-hydroxide-carbonate + 0.05% 164 77 of Zn-oxide0.05% of Zn-hydroxide-carbonate + 0.05% 86 70.5 of Mg-hydroxide 0.05% ofhydrotalcite (® REHEIS) + 0.05% 104 68.5 of Mg-stearate 0.05% ofhydrotalcite (® REHEIS) + 0.05% 131 69 of Zn-stearate 0.05% of dolomite(® Microdol Super) + 78 62.5 0.05% of Zn-stearate 0.05% of dolomite(® Microdol Super) + 66 62 0.05% of Mg-stearate 0.05% of dolomite(® Microdol Super) + 74 63 0.05% of Zn-oxide 0.05% of dolomite(® Microdol Super) + 60 56.5 0.05% of Mg-hydroxide

TABLE 2 Sterically hindered amine compound: 0.1% of the compound 84-1T_(0.2 measured) T_(0.2 calculated) Coadditiv (kLy) (kLy) 0.1% ofhydrotalcite (® DHT-4A) 144 0.1% of Mg-hydroxide-carbonate 124 0.1% ofZn-hydroxide-carbonate 136 0.1% of Mg-stearate 140 0.1% of Zn-stearate164 0.1% of Mg-acetylacetonate 97 0.1% of Mg-oxide 171 0.1% of Zn-oxide258 0.1% of Mg-hydroxide 165 0.1% of hydrotalcite (® REHEIS) 133 0.1% ofdolomite (® Microdol Super) 80 0.05% of Mg-stearate + 0.05% 174 142 ofhydrotalcite (® DHT-4A) 0.05% of Zn-stearate + 0.05% 232 154 ofhydrotalcite (® DHT-4A) 0.05% of Mg-acetylacetonate + 0.05% 146 120.5 ofhydrotalcite (® DHT-4A) 0.05% of Mg-oxide + 0.05% 210 157.5 ofhydrotalcite (® DHT-4A) 0.05% of Mg-hydroxide + 0.05% 192 154.5 ofhydrotalcite (® DHT-4A) 0.05% of Zn-hydroxide-carbonate + 0.05% 183 138of Mg-stearate 0.05% of Zn-hydroxide-carbonate + 0.05% 154 150 ofZn-stearate 0.05% of Zn-hydroxide-carbonate + 0.05% 151 116.5 ofMg-acetylacetonate 0.05% of Zn-hydroxide-carbonate + 0.05% 204 153.5 ofMg-oxide 0.05% of Zn-hydroxide-carbonate + 0.05% 266 197 of Zn-oxide0.05% of Zn-hydroxide-carbonate + 0.05% 171 150.5 of Mg-hydroxide 0.05%of hydrotalcite (® REHEIS) + 0.05% 151 136.5 of Mg-stearate 0.05% ofhydrotalcite (® REHEIS) + 0.05% 177 148.5 of Zn-stearate 0.05% ofhydrotalcite (® REHEIS) + 0.05% 167 152 of Mg-oxide 0.05% of dolomite(® Microdol Super) + 133 122 0.05% of Zn-stearate 0.05% of dolomite(® Microdol Super) + 190 169 0.05% of Zn-oxide

TABLE 3 T_(0.2 measured) T_(0.2 calculated) Coadditiv (kLy) (kLy) 0.1%of hydrotalcite (® DHT-4A) 127 0.1% of Mg-hydroxide-carbonate 122 0.1%of Zn-hydroxide-carbonate 121 0.1% of Mg-stearate 216 0.1% ofZn-stearate 200 0.1% of Mg-acetylacetonate 202 0.1% of Mg-oxide 176 0.1%of Zn-oxide 70 0.1% of Mg-hydroxide 146 0.1% of hydrotalcite (® REHEIS)144 0.1% of dolomite (® Microdol Super) 77 0.1% of Mg-acetate 186 0.1%of Zn-acetylacetonate 68 0.05% of hydrotalcite (® DHT-4A) + 236 171.50.05% of Mg-stearate 0.05% of hydrotalcite (® DHT-4A) + 196 163.5 0.05%of Zn-stearate 0.05% of hydrotalcite (® DHT-4A) + 230 164.5 0.05% ofMg-acetylacetonate 0.05% of hydrotalcite (®DHT-4A) + 165 151.5 0.05% ofMg-oxide 0.05% of Zn-hydroxide-carbonate + 224 168.5 0.05% ofMg-stearate 0.05% of Zn-hydroxide-carbonate + 248 161.5 0.05% ofMg-acetylacetonate 0.05% of Zn-hydroxide-carbonate + 184 148.5 0.05% ofMg-oxide 0.05% of Zn-hydroxide-carbonate + 144 95.5 0.05% of Zn-oxide0.05% of Zn-hydroxide-carbonate + 165 133.5 0.05% of Mg-hydroxide 0.05%of hydrotalcite (® REHEIS) + 304 180 0.05% of Mg-stearate 0.05% ofhydrotalcite (® REHEIS) + 288 172 0.05% of Zn-stearate 0.05% of dolomite(® Microdol Super) + 192 146.5 0.05% of Mg-stearate 0.05% of dolomite(® Microdol Super) + 172 138.5 0.05% of Zn-stearate 0.05% ofMg-stearate + 236 208 0.05% of Zn-stearate 0.05% of Mg-stearate + 180142 0.05% of Zn-acetylacetonate 0.05% of Mg-stearate + 254 196 0.05% ofMg-oxide 0.05% of Mg-stearate + 158 143 0.05% of Zn-oxide 0.05% ofMg-stearate + 252 181 0.05% of Mg-hydroxide 0.05% of Zn-stearate + 216193 0.05% of Mg-acetate 0.05% of Zn-stearate + 240 188 0.05% of Mg-oxide0.05% of Zn-stearate + 228 173 0.05% of Mg-hydroxide 0.05% ofMg-acetylacetonate + 228 135 0.05% of Zn-acetylacetonate 0.05% ofMg-acetylacetonate + 256 189 0.05% of Mg-oxide 0.05% ofMg-acetylacetonate + 176 136 0.05% of Zn-oxide 0.05% ofMg-acetylacetonate + 252 174 0.05% of Mg-hydroxide 0.05% ofZn-acetylacetonate + 156 122 0.05% of Mg-oxide 0.05% ofZn-acetylacetonate + 83 69 0.05% of Zn-oxide 0.05% of Mg-oxide + 146 1230.05% of Zn-oxide Sterically hindered amine compound: 0.05% of thecompound 81 UV absorber: 0.05% of the compound of the formula

TABLE 4 Polymer and exposure period are different from those used forTable 3. T_(0.2 measured) T_(0.2 calculated) Coadditiv (kLy) (kLy) 0.2%of hydrotalcite (® DHT-4A) 185 0.2% of Mg-stearate 196 0.2% of Mg-oxide164 0.1% of Mg-stearate + 254 190.5 0.1% of hydrotalcite (® DHT-4A) 0.1%of Mg-stearate + 234 180 0.1% of Mg-oxide Sterically hindered aminecompound: 0.05% of the compound 81) UV absorber: 0.05% of the compoundof the formula

EXAMPLE II Light Stabilization of Injection Molded 2 Mm PolypropylenePlaques

100 parts of polypropylene powder (melt flow index: 2.4 g/10 min at 230°C. and 2160 g) are blended in a barrel mixer with 0.05 parts ofpentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.05 parts oftris[2,4-di-tert-butylphenyl] phosphite, and the stabilizer systemindicated in Tables 5 and 6. Then, the blend is compounded in anextruder at temperatures of 200 °–220° C. The granules obtained onextrusion and granulation are transformed into 2 mm thick plaques at 240°–260° C. in an automatic injection molding machine.

The plaques are mounted on sample holders and exposed in aWEATHER-OMETER Ci 65 (black panel temperature 63±2° C., withoutwater-spraying). Periodically, these samples are removed from theexposure apparatus and their carbonyl content is measured with aninfrared spectrophotometer. The exposure time corresponding to formationof a carbonyl absorbance of 0.5 is a measure for the stabilizingefficiency of the light stabilizer.

The values obtained are summarized in Tables 5 and 6.

The determination of the synergistic effect of the two coadditivs iscarried out as described in Example I.

TABLE 5 T_(0.5 measured) (hours to 0.5 carbonyl absorbance) 0.1% of Mg-stea- rate + 0.05% of 0.1% of 0.2% of the sterically hydrotalcitehydrotalcite hindered amine (® DHT- 0.2% of (® DHT- compound 4A)Mg-stearate 4A) T_(0.5 calculated) Compound 13 3520 3060 1880 2470Compound 10 3420 3300 2000 2650 Compound 14 3720 3360 1880 2620 Compound2700 2700 1620 2160 36-b Compound 2780 2920 1720 2320 36-a Compound 632340 2280 1900 2090 Compound 2420 2300 1680 1990 49-e Compound 2540 23201920 2120 80-a Compound 2840 3040 1980 2510 49-a-l UV absorber: 0.05% ofthe compound of the formula

TABLE 6 T_(0.5 measured) 0.05% of (hours to 0.5 carbonyl absorbance) the0.2% sterically of 0.2% of hindered 0.1% of Mg-stearate + Mg-hydrotalcite amine 0.1% of hydrotalcite stea- (® DHT- compound(® DHT-4A) rate 4A) T_(0.5 calculated) Compound 3320 2840 1300 2070 81Compound 2400 2140 1920 2030 84-1 Compound 2560 2420 2100 2260 76Compound 2180 2000 2000 2000 92 Compound 2160 2000 1360 1680 97-IICompound 3080 3080 2600 2840 101-I Compound 2480 2300 2280 2290 100-AMixture 2080 2000 1900 1950 of compounds 96-I and 96-II UV absorber:0.05% of the compound of the formula

EXAMPLE III Light Stabilization of Polypropylene Tapes

100 parts of polypropylene powder (melt flow index: 2 g/10 min at 230°C. and 2160 g) are blended in a barrel mixer with 0.05 parts ofpentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.05 parts oftris[2,4-di-tert-butylphenyl] phosphite, 0.1 parts of Ca stearate, 0.4parts of titanium dioxide (rutile) and the stabilizer system indicatedin Table 7. Then, the blend is compounded in an extruder at temperaturesof 180 °–220° C. The granules obtained on extrusion and granulation aretransformed into films at 220 °–260° C. in a second extruder equippedwith a flat sheet die. The films are cut into ribbons which are drawn toachieve a stretch ratio of 1:6. The tapes obtained with this procedureare finally 50 μm thick and 2.5 mm wide.

The tapes are mounted without tension on sample holders and exposed in aWEATHER-OMETER Ci 65 (black panel temperature 63±2° C., withoutwater-spraying). Periodically, the tensile strength of the exposed tapesis measured. The exposure time corresponding to a loss of 50% (T₅₀) ofthe initial tensile strength is a measure for the stabilizing efficiencyof the stabilizer system.

The values obtained are summarized in Table 7.

The determination of the synergistic effect of the two coadditivs iscarried out as described in Example I.

TABLE 7 T_(50 measured) (hours to 50% retained tensile strength) 0.05%of Mg-stearate + 0.05% 0.1% of Sterically hindered of hydrotalcite 0.1%of hydrotalcite amine compound (® DHT-4A) Mg-stearate (® DHT-4A)T_(50 calculated) 0.05% of the compound 13 2440 1150 1920 1535 0.10% ofthe compound 10 7200 2760 4300 3530 0.20% of the compound 14 15000 700010000 8500

EXAMPLE IV Light Stabilization of Polypropylene Copolymer Films

100 parts of unstabilized polypropylene copolymer powder (melt flowindex: 3.8 g/10 minutes at 230° C. and 2160 g) are homogenized at 200°C. for 10 minutes in a ®Brabender plastograph with 0.05 parts ofpentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate},0.1 parts of tris(2,4-di-tert-butylphenyl) phosphite and the stabilizersystem indicated in Tables 8 and 9.

The material thus obtained is compression molded in a laboratory pressbetween two aluminum foils for 6 minutes at 260° C. to a 0.5 mm thickfilm which is cooled immediately to room temperature in a water-cooledpress. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and areexposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C.,without water-spraying). Periodically, these samples are removed fromthe exposure apparatus and their carbonyl content is measured with aninfrared spectrophotometer.

The exposure time corresponding to formation of a carbonyl absorbance of0.1 is a measure for the stabilizing efficiency of the stabilizersystem. The values obtained are summarized in the following Tables 8 and9.

The determination of the synergistic effect of the two coadditivs iscarried out as described in Example I.

TABLE 8 T_(0.1 measured) 0.1% of (hours to 0.1 carbonyl absorbance) the0.1% sterically of 0.1% of hindered 0.5% of Mg stearate + Mghydrotalcite amine 0.5% of hydrotalcite stea- (® DHT- compound(® DHT-4A) rate 4A) T_(0.1 calculated) Compound 3260 2100 3340 2720 84-1Compound 2480 2060 2680 2370 84-2 Compound 2600 2520 2560 2540 97-IICompound 2040 1580 2340 1960 99-I Compound 1300 900 1410 1155 99-IICompound 3760 3200 3460 3330 100-A Mixture 2900 2480 3120 2800 of thecompounds 96-I and 96-Il Compound 840 570 930 750 99-III 0.1% of Castearate UV absorber: 0.1% of

TABLE 9 T_(0.1 measured) 0.1% of (hours to 0.1 carbonyl absorbance) the0.1% sterically 0.05% of of 0.1% of hindered Mg stearate + Mghydrotalcite amine 0.05% of hydrotalcite stea- (® DHT- compound(® DHT-4A) rate 4A) T_(0.1 calculated) Compound 6800 6960 6120 6540 13Compound 5880 5480 5920 5700 14 Compound 3140 2600 3480 3040 63 Compound4000 3760 3200 3480 36-b Compound 3400 2900 2700 2800 80-a Compound 50804720 4800 4760 49-d Compound 6520 6760 5840 6300 49-a-I Compound 65605840 5640 5740 49-a-II Compound 8040 8200 7520 7860 5 Compound 3440 29203320 3120 105 Compound 3160 3080 2980 3030 36-d Compound 2780 2320 25802450 69-a 0.1% of Ca stearate UV absorber: 0.1% of

EXAMPLE V Light stabilization of High Density Polyethylene Films

100 parts of unstabilized high density polyethylene powder (density:0.964 g/cm³, melt flow index: 5.0 g/10 minutes at 190° C. and 2160 g)are homogenized at 180° C. for 10 minutes in a ®Brabender plastographwith 0.03 parts of octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, and the stabilizersystem indicated in Table 10.

The material thus obtained is compression molded in a laboratory pressbetween two aluminum foils for 6 minutes at 210° C. to a 0.5 mm thickfilm which is cooled immediately to room temperature in a water-cooledpress. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and areexposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C.,without water-spraying). Periodically, these samples are removed fromthe exposure apparatus and their carbonyl content is measured with aninfrared spectrophotometer.

The exposure time corresponding to formation of a carbonyl absorbance of0.1 is a measure for the efficiency of the stabilizer system. The valuesobtained are summarized in Table 10.

The determination of the synergistic effect of the two coadditivs iscarried out as described in Example I.

TABLE 10 T_(0.1 measured) 0.1% of (hours to 0.1 carbonyl absorbance) thesterically 0.05% of Mg stearate + 0.1% of hindered amine 0.05% ofhydrotalcite 0.1% of hydrotalcite compound (® DHT-4A) Mg stearate(® DHT-4A) T_(0.1 calculated) Compound 81 10160 9160 4720 6940 Compound84-1 16270 15930 13590 14760 Compound 101-I 18660 18180 15580 16880Compound 13 10580 10810 5110 7960

EXAMPLE VI Light Stabilization of High Density Polyethylene Films

100 parts of high density polyethylene powder (density: 0.961 g/cm³;melt flow index:

6.0 g/10 minutes at 190° C. and 2160 g) stabilized with 0.05 parts ofoctadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.05parts of bis{2,4-di-tert-butylphenyl}-pentaerythrityl diphosphite arehomogenized at 180° C. for 10 minutes in a ®Brabender plastograph withthe stabilizer system indicated in Table 11.

The material thus obtained is compression molded in a laboratory pressbetween two aluminum foils for 6 minutes at 210° C. to a 0.5 mm thickfilm which is cooled immediately to room temperature in a water-cooledpress. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and areexposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C.,without water-spraying). Periodically, these samples are removed fromthe exposure apparatus and their carbonyl content is measured with aninfrared spectrophotometer.

The exposure time corresponding to formation of a carbonyl absorbance of0.1 is a measure for the efficiency of the stabilizer system. The valuesobtained are summarized in Table 11.

The determination of the synergistic effect of the two coadditivs iscarried out as described in Example I.

TABLE 11 T_(0.1 measured) 0.1% of (hours to 0.1 carbonyl absorbance) thesterically 0.05% of Mg stearate + 0.1% of hindered amine 0.05% ofhydrotalcite 0.1% of hydrotalcite compound (® DHT-4A) Mg stearate(® DHT-4A) T_(0.1 calculated) Compound 84-1 10560 7760 10960 9360Compound 101-I 2800 1160 3400 2280 Compound 100-A 10160 8720 11280 10000Compound 13 4160 3480 4480 3980

EXAMPLE VII Light Stabilization of Polypropylene Homopolymer Films

100 parts of unstabilized polypropylene powder (melt flow index: 3 g/10minutes at 230°C. and 2160 g) are homogenized at 200° C. for 10 minutesin a Brabender plastograph with 0.05 parts of pentaerythrityltetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 0.1 parts oftris{2,4-di-tert-butylphenyl} phosphite and the stabilizer systemindicated in Tables 12 and 13.

The material thus obtained is compression molded in a laboratory pressbetween two aluminum foils for 6 minutes at 260° C. to a 0.5 mm thickfilm which is cooled immediately to room temperature in a water-cooledpress. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and areexposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C.,without water-spraying). Periodically, these samples are removed fromthe exposure apparatus and their carbonyl content is measured with aninfrared spectrophotometer.

The exposure time corresponding to formation of a carbonyl absorbance of0.1 is a measure for the efficiency of the stabilizer system. The valuesobtained are summarized in Tables 12 and 13.

The determination of the synergistic effect of the two coadditivs iscarried out as described in Example I.

TABLE 12 T_(0.1 measured) 0.1% of (hours to 0.1 carbonyl absorbance) thesterically 0.05% of Mg stearate + 0.1% of hindered amine 0.05% ofhydrotalcite 0.1% of hydrotalcite compound (® DHT-4A) Mg stearate(® DHT-4A) T_(0.1 calculated) Compound 81 2120 2440 970 1705 Compound84-1 1600 1560 1510 1535 Compound 101-I 2520 2360 1980 2170

TABLE 13 T_(0.1 measured) 0.1% of (hours to 0.1 carbonyl absorbance) the0.1% sterically 0.05% of of 0.1% of hindered Mg stearate + Mghydrotalcite amine 0.05% of hydrotalcite stea- (® DHT- compound(® DHT-4A) rate 4A) T_(0.1 calculated) Compound 3160 3160 1540 2350 81Compound 2420 2440 2160 2300 84-1 Compound 3220 3300 2860 3080 101-ICompound 3660 2700 2580 2640 100-A UV absorber: 0.1% of

1. A composition comprising a polyolefin subject to degradation inducedby light, heat or oxidation and a stabilizer mixture containing (A) asterically hindered amine compound, and (B) 0.005 to 1%, relative to theweight of the polyolefin, of two different compounds selected from thegroup consisting of an organic salt of Zn, an inorganic salt of Zn,zinc-oxide, zinc-hydroxide an organic salt of Mg, an inorganic salt ofMg, magnesium-oxide and magnesium-hydroxide; the weight ratio of the twodifferent compounds being 1:5 to 5:1; with the provisos that (1) thestabilizer mixture is essentially free of perchloric acid, and (2) thetwo compounds in component (B) are different from the combination ZnOand Zn stearate and the combination ZnO and hydrotalcite.
 2. Acomposition mixture according to claim 1 wherein the sterically hinderedamine compound corresponds to a compound containing at least one groupof the formula (I) or (II)

in which G is hydrogen or methyl, and G₁ and G₂, independently of oneanother, are hydrogen, methyl or together are a substituent ═O.
 3. Acomposition according to claim 1 wherein the sterically hindered aminecompound corresponds to

with m₁ being a number from 2 to 50,

with m₄ being a number from 2 to 50,

with m₄ being a number from 2 to 50,

with m₄ being a number from 2 to 50,

with m₁₆ being a number from 2 to 50,

with m₁₆* being a number from 2 to 50,

with m₁₇ being a number from 1 to 50,

with m₁₉ being a number from 1 to 50,

with m₁₉ being a number from 1 to 50,

with m₁₉ being a number from 1 to 50, a product obtainable by reactingan intermediate product, obtained by reaction of a polyamine of theformula (100a-I) with cyanuric chloride, with a compound of the formula(100b-I),

with m₂₁ being a number from 1 to 50, or


4. A composition according to claim 1 wherein the two differentcompounds of component (B) are selected from the group consisting ofhydrotalcite, dolomite, Zn-hydroxide-carbonate, Mg-hydroxide-carbonate,Zn-oxide, Mg-oxide, Zn-hydroxide, Mg-hydroxide, Zn-stearate,Mg-stearate, Zn-acetylacetonate, Mg-acetylacetonate, Zn-acetate andMg-acetate.
 5. A composition according to claim 1 wherein the twodifferent compounds in component (B) are Mg-stearate and hydrotalcite,Zn-stearate and hydrotalcite, Mg-stearate and Zn-stearate, Zn-stearateand Mg-oxide, or Mg-stearate and Mg-hydroxide.
 6. A compositionaccording to claim 1, containing additionally (C1) a pigment or (C2) anUV absorber or (C3) a pigment and an UV absorber.
 7. A compositionaccording to claim 6 wherein the pigment is titanium dioxide, zincoxide, carbon black, cadmium sulfide, cadmium selenide, chromium oxide,iron oxide, lead oxide, an azo pigment, an anthraquinone, aphthalocyanine, a tetrachloroisoindolinone, a quinacridone, anisoindoline, a perylene or a pyrrolopyrrole.
 8. A composition accordingto claim 6 wherein the UV absorber is a2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone, an ester ofsubstituted or unsubstituted benzoic acid, an acrylate, an oxamide, a2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of resorcinol or aformamidine.
 9. A composition according to claim 1 which additionallycontains an organic salt of Ca, an inorganic salt of Ca, Ca-oxide orCa-hydroxide.
 10. A composition according to claim 1 wherein thepolyolefin is polyethylene, polypropylene, a polyethylene copolymer or apolypropylene copolymer.
 11. A method for stabilizing a polyolefinagainst degradation induced by light, heat or oxidation, which comprisesincorporating into the polyolefin a stabilizer mixture according toclaim 1; with the provisos that the (1) the stabilizer mixture isessentially free of perchloric acid; (2) the two compounds in component(B) are different from the combination ZnO and Zn-stearate and thecombination ZnO and hydrotalcite.